FR2915743A1 - COMPOSITE OF NANOTUBES OR NANOFIBERS ON BETA-SIC FOAM - Google Patents
COMPOSITE OF NANOTUBES OR NANOFIBERS ON BETA-SIC FOAM Download PDFInfo
- Publication number
- FR2915743A1 FR2915743A1 FR0703155A FR0703155A FR2915743A1 FR 2915743 A1 FR2915743 A1 FR 2915743A1 FR 0703155 A FR0703155 A FR 0703155A FR 0703155 A FR0703155 A FR 0703155A FR 2915743 A1 FR2915743 A1 FR 2915743A1
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- France
- Prior art keywords
- sic
- nanofibers
- nanotubes
- catalyst
- carbon nanotubes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000002071 nanotube Substances 0.000 title claims abstract description 19
- 239000006260 foam Substances 0.000 title claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 7
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- -1 C 3 hydrocarbons Chemical class 0.000 claims 1
- 239000007792 gaseous phase Substances 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 229910010271 silicon carbide Inorganic materials 0.000 description 63
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000011863 silicon-based powder Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021431 alpha silicon carbide Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 108091028606 miR-1 stem-loop Proteins 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZARVOZCHNMQIBL-UHFFFAOYSA-N oxygen(2-) titanium(4+) zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4] ZARVOZCHNMQIBL-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
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- B01J23/74—Iron group metals
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- B01J27/224—Silicon carbide
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
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- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07—ORGANIC CHEMISTRY
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Abstract
L'invention concerne un procédé de fabrication d'un composite comportant des nanofibres ou nanotubes sur un substrat poreux de SiC, ledit procédé comportant les étapes suivantes :(d) On incorpore dans ledit substrat poreux de SiC, ou dans un précurseur de SiC, un catalyseur de croissance de nanotubes ou nanofibres ;(e) On fait croître des nanotubes ou nanofibres de carbone à partir d'un mélange comprenant au moins un hydrocarbure et de l'hydrogène ;(f) Optionnellement, on transforme lesdits nanotubes ou nanofibres en carbone en nanofibres de SiC.Ce produit composite peut être utilisé comme catalyseur ou support de catalyseur.The invention relates to a method for manufacturing a composite comprising nanofibers or nanotubes on a porous SiC substrate, said process comprising the following steps: (d) embedded in said porous SiC substrate, or in an SiC precursor, a nanotube or nanofiber growth catalyst; (e) carbon nanotubes or nanofibers are grown from a mixture comprising at least one hydrocarbon and hydrogen; (f) optionally, said nanotubes or nanofibers are converted into SiC nanofibers carbon.This composite product can be used as catalyst or catalyst support.
Description
Composite de nanotubes ou nanofibres sur mousse de R-SiC Domaine techniqueComposite of nanotubes or nanofibres on R-SiC foam Technical field
de l'invention L'invention concerne le domaine technique des nanofibres, et plus spécialement des nanofibres de carbone ou de SiC déposées sur un substrat constitué de mousse de 13-SiC. Les composites ainsi formés ont des applications comme catalyseur ou support de catalyseur. The invention relates to the technical field of nanofibers, and more particularly carbon nanofibers or SiC deposited on a substrate made of 13-SiC foam. The composites thus formed have applications as catalyst or catalyst support.
Etat de la technique On connaît depuis longtemps les nanotubes et nanofibres en carbone. Ces matériaux ont des propriétés catalytiques intéressantes. Ils se présentent sous la forme de longues structures très fines, souvent d'un aspect duveteux, qui ont un volume spécifique très élevé, et qui sont de ce fait difficiles à manipuler. La crainte est qu'ils puissent être nuisibles pour la santé, notamment par inhalation. Des grandes précautions sont aujourd'hui mises en oeuvre lors de leur production, leur manipulation, leur conditionnement et leur transport. Par ailleurs, l'utilisation de catalyseurs ou supports de catalyseurs se présentant sous forme de particules ou fibres libres de petite taille (telles qu'une poudre ou des fibres) pose le problème de la perte de charge des gaz qui sont mis en contact avec ces particules ou fibres. Par ailleurs, il faut empêcher que ces particules ou fibres ne soient emportées par le flux gazeux ou liquide lors de leur utilisation en catalyse. Fixer des nanotubes ou nanofibres sur divers supports permet d'éviter ce problème. A titre d'exemple, la demande de brevet FR 2 832 649 (SICAT) décrit la croissance de nanotubes ou nanofibres de carbone sur divers supports tels que le feutre de carbone, l'alumine, la silice, l'oxyde de titane, l'oxyde de zirconium ou la cordiérite. Mais les nanotubes et nanofibres en carbone ont eux-mêmes l'inconvénient d'être sensibles à l'oxydation, ce qui en pratique limite leur utilisation comme catalyseur ou support de catalyseur. State of the art Carbon nanotubes and nanofibers have long been known. These materials have interesting catalytic properties. They come in the form of long, very thin structures, often of a fluffy appearance, which have a very high specific volume, and which are therefore difficult to handle. The fear is that they can be harmful to health, including inhalation. Great precautions are currently used during their production, handling, packaging and transport. Furthermore, the use of catalysts or catalyst supports in the form of small particles or free fibers (such as a powder or fibers) raises the problem of the pressure drop of the gases which are brought into contact with these particles or fibers. Moreover, it is necessary to prevent these particles or fibers from being swept away by the gaseous or liquid flow during their use in catalysis. Fixing nanotubes or nanofibers on various media avoids this problem. By way of example, patent application FR 2,832,649 (SICAT) describes the growth of carbon nanotubes or nanofibers on various supports such as carbon felt, alumina, silica, titanium zirconium oxide or cordierite. But carbon nanotubes and nanofibers themselves have the disadvantage of being sensitive to oxidation, which in practice limits their use as catalyst or catalyst support.
On connaît également des nanofibres de SiC qui peuvent être déposées, en très faible quantité et simultanément avec des nanotubes de carbone, sur un substrat de silicium monocristallin Si(001) revêtu d'un film de nickel d'une épaisseur de quelques dizaines de nanomètres (voir par exemple l'article Simultaneous growth of silicon carbide nanorods and carbon nanotubes by chemical vapor deposition par B.Q. Wei et al., Chemical Physics Lettres 354 (2002), p. 264-268). Par le dépôt d'une couche mince de silicium amorphe sur des nanotubes de carbone suivi d'un recuit à 1200 C, seule est formée une couche de SiC sur les nanotubes de carbone (voir J.W. Lui et al., Synthetis of SiC nanofibers by annealing carbon nanotubes covered with Si , Chemical Physics Letters 348, p. 357 ù 360 (2001)). La formation de nanofibres de SiC a aussi été décrite lors du recuit de nanotubes de carbone sur un substrat de silicium (E. Munoz et al., Synthetis of SiC nanorods from sheets of single-walled carbon nanotubes , Chemical Physics Letters 359 (2002), p. 397-402). Une autre méthode pour former des nanofibres de 13-SiC a été décrite dans l'article Structural tansformation of carbon nanotubes to silicon carbide nanorods or microcrystals by the reaction with different silicon sources un rf indiced CVD reactor par Y.H. Mo et al. (Synthetic Metals 140 (2004), 309-315) : on fait réagir des nanotubes de carbone déposés sur un substrat de silicium avec un mélange de SiH4 + C3H8 + H2 ou de TMS (tétraméthylsilane) + H2 à une température de 1250 C. SiC nanofibers are also known which can be deposited, in a very small quantity and simultaneously with carbon nanotubes, on a Si (001) monocrystalline silicon substrate coated with a nickel film having a thickness of a few tens of nanometers (See for example the article Simultaneous growth of silicon carbide nanorods and carbon nanotubes by chemical vapor deposition by BQ Wei et al., Chemical Physics Letters 354 (2002), pp. 264-268). By depositing a thin layer of amorphous silicon on carbon nanotubes followed by annealing at 1200 ° C., only one layer of SiC is formed on the carbon nanotubes (see JW Lui et al., Synthetis of SiC nanofibers by annealing carbon nanotubes covered with Si, Chemical Physics Letters 348, pp 357-160 (2001)). The formation of SiC nanofibers has also been described during the annealing of carbon nanotubes on a silicon substrate (E. Munoz et al., Synthetis of SiC nanorods from sheets of single-walled carbon nanotubes, Chemical Physics Letters 359 (2002) , pp. 397-402). Another method for forming 13-SiC nanofibers has been described in the article Structural tansformation of carbon nanotubes to silicon carbide nanorods or microcrystals by the reaction with different silicon sources a rf indiced CVD reactor by Y.H. Mo et al. (Synthetic Metals 140 (2004), 309-315): carbon nanotubes deposited on a silicon substrate are reacted with a mixture of SiH4 + C3H8 + H2 or TMS (tetramethylsilane) + H2 at a temperature of 1250.degree.
Par ailleurs, la demande de brevet US 2006/0115648 ( Nanofibres and process for making the same ) décrit la fabrication de nanofibres dites composites de type SiC + C , SiC + TiC ou SiC + A1N d'une longueur pouvant atteindre plusieurs centaines de mètres par un procédé de fusion et extrusion à travers un petit trou du four à une température pouvant atteindre 1600 C. La structure de ces fibres n'est pas décrite. La demande de brevet US 2004/0202599 ( Method of producing nanometer silicon carbide material ) décrit la fabrication de nanofibres de SiC à partir de poudre de SiC en présence d'un catalyseur (Al ou Fe) à une température comprise entre 1300 C et 2000 C dans une atmosphère d'argon. Ces fibres ont un diamètre minimal de 5 nm et une longueur maximale de 5 m. La demande de brevet US 2005/0255033 ( Laser fabrication of continuous nanofibres ) décrit la fabrication de nanofibres de SiC par un procédé d'évaporation induite par faisceau laser, en présence d'un métal de transition agissant comme catalyseur à une température comprise entre 500 C et 1400 C.. Furthermore, the patent application US 2006/0115648 (nanofibers and process for making the same) describes the manufacture of so-called composite nanocrystals of SiC + C, SiC + TiC or SiC + A1N type with a length of up to several hundred meters. by a process of melting and extruding through a small hole of the furnace at a temperature up to 1600 C. The structure of these fibers is not described. The patent application US 2004/0202599 (Method of producing nanometer silicon carbide material) describes the production of SiC nanofibers from SiC powder in the presence of a catalyst (Al or Fe) at a temperature of between 1300 C and 2000 C in an argon atmosphere. These fibers have a minimum diameter of 5 nm and a maximum length of 5 m. The patent application US 2005/0255033 (Laser manufacturing of continuous nanofibers) describes the production of SiC nanofibers by a laser beam evaporation method, in the presence of a transition metal acting as a catalyst at a temperature of between 500 C and 1400 C.
Description détaillée de l'invention Detailed description of the invention
Le problème est résolu selon l'invention en faisant croître les nanotubes ou nanofibres directement sur un support de carbure de silicium, ou sur un précurseur de carbure de silicium. Un support particulièrement utile est le carbure de silicium à haute surface spécifique, et notamment le 13-SiC . Ce matériau est connu en tant que tel. Il peut être obtenu par la réaction entre des vapeurs de SiO avec du carbone réactif à une température comprise entre 1100 C et 1400 C (procédé Ledoux, voir EP 0 313 480 B1), ou par un procédé dans lequel un mélange d'un polymère liquide ou pâteux et d'une poudre de silicium est réticulé, carbonisé et carburé à une température comprise entre 1000 C et 1400 C (procédé Dubots, voir EP 0 440 569 B1 ou EP 0 952 889 B l). On connaît par ailleurs les mousses de 13-SiC, qui peuvent être obtenues par une variante du procédé Dubots, comprenant l'imprégnation d'une mousse polyuréthane avec une suspension d'une poudre de silicium dans une résine organique (procédé Prin, voir EP 0 624 560 B1, EP 0 836 882 B1 ou EP 1 007 207 Al). Tous ces supports, et d'autres types de SiC, qu'il s'agisse de a-SiC ou, de manière préférée, de 13-SiC, peuvent être utilisés dans le cadre de la présente invention. A titre d'exemple, on peut utiliser des monolithes, des extrudés ou des mousses de SiC, avantageusement du (3-SiC. La surface spécifique du support est préférentiellement supérieure à 5 m2/g, et plus préférentiellement supérieure à 10 m2/g. La mousse de 13-SiC, préparée selon le procédé Prin référencée ci-dessus ou par tout autre procédé, avec une surface spécifique supérieure à 10 m2/g constitue un support particulièrement préféré pour la réalisation de la présente invention. The problem is solved according to the invention by growing the nanotubes or nanofibers directly on a silicon carbide support, or on a precursor of silicon carbide. A particularly useful support is silicon carbide with a high specific surface area, and in particular 13-SiC. This material is known as such. It can be obtained by the reaction between SiO 2 vapors with reactive carbon at a temperature of between 1100 ° C. and 1400 ° C. (Ledoux process, see EP 0 313 480 B1), or by a process in which a mixture of a polymer liquid or pasty and a silicon powder is crosslinked, carbonized and carburized at a temperature between 1000 C and 1400 C (Dubots process, see EP 0 440 569 B1 or EP 0 952 889 B 1). 13-SiC foams, which can be obtained by a variant of the Dubots process, including the impregnation of a polyurethane foam with a suspension of a silicon powder in an organic resin (Prin process, see EP) are also known. 0 624 560 B1, EP 0 836 882 B1 or EP 1 007 207 A1). All these supports, and other types of SiC, whether a-SiC or, preferably, 13-SiC, may be used within the scope of the present invention. By way of example, it is possible to use monoliths, extrudates or foams of SiC, advantageously (3-SiC), the specific surface area of the support is preferably greater than 5 m 2 / g, and more preferably greater than 10 m 2 / g. The 13-SiC foam, prepared according to the Prin method referenced above or by any other method, with a specific surface area greater than 10 m 2 / g constitutes a particularly preferred support for the embodiment of the present invention.
Le procédé selon l'invention permettant de faire croître des nanotubes ou nanofibres de carbone, ou des nanotubes ou nanofibres de SiC sur un support poreux de SiC implique les étapes suivantes : The process according to the invention for growing carbon nanotubes or nanofibers, or nanotubes or nanofibers of SiC on a porous SiC support involves the following steps:
(a) Incorporation d'un catalyseur de croissance de nanotubes ou nanofibres dans le 30 support poreux de SiC. (a) Incorporation of a nanotube or nanofiber growth catalyst into the porous SiC support.
Ce catalyseur est destiné à favoriser la croissance des nanotubes ou nanofibres de carbone. Avantageusement, du nickel est utilisé, notamment pour fabriquer des 3 nanofibres de carbone, ou du fer, du cobalt ou un mélange de fer et de cobalt pour fabriquer des nanotubes en carbone. Peut également être utilisé tout autre mélange binaire ou ternaire de ces trois éléments. Nous décrivons ici un mode de réalisation typique pour cette étape. Il est possible de procéder par imprégnation du support poreux de SiC avec une solution d'un précurseur de phase active. Cette solution peut être par exemple une solution aqueuse ou alcoolique. Le précurseur peut être un sel d'un métal de transition, par exemple du Ni(NO3)2. La charge en métal est avantageusement comprise entre 0,4% massique et 3% massique, et de préférence entre 0,5% et 2%. Après l'imprégnation, on sèche à l'étuve, de préférence à une température comprise entre 80 C et 120 C pendant 1 à 10 heures, puis on calcine sous air ou sous atmosphère inerte à une température comprise entre 250 C et 500 C. Le précurseur de phase active est alors transformé en phase active, préférentiellement par une réduction sous gaz réducteur à une température appropriée, par exemple comprise entre 250 C et 500 C sous hydrogène. (b) Croissance de nanotubes ou nanofibres de carbone à partir d'un mélange comprenant au moins un hydrocarbure et de l'hydrogène. This catalyst is intended to promote the growth of carbon nanotubes or nanofibers. Advantageously, nickel is used, in particular to make 3 carbon nanofibers, or iron, cobalt or a mixture of iron and cobalt to make carbon nanotubes. Any other binary or ternary mixture of these three elements may also be used. We describe here a typical embodiment for this step. It is possible to impregnate the porous SiC support with a solution of an active phase precursor. This solution may be for example an aqueous or alcoholic solution. The precursor may be a salt of a transition metal, for example Ni (NO 3) 2. The metal filler is advantageously between 0.4% by mass and 3% by mass, and preferably between 0.5% and 2%. After the impregnation, it is dried in an oven, preferably at a temperature between 80 C and 120 C for 1 to 10 hours, and then calcined in air or in an inert atmosphere at a temperature between 250 C and 500 C. The active phase precursor is then converted into the active phase, preferably by reduction under a reducing gas to a suitable temperature, for example between 250 ° C. and 500 ° C. under hydrogen. (b) Growth of carbon nanotubes or nanofibers from a mixture comprising at least one hydrocarbon and hydrogen.
L'hydrocarbure est un hydrocarbure en Cl à c 10 aliphatique, oléfinique, acétylénique ou aromatique. Les hydrocarbures aliphatiques, oléfiniques ou acétyléniques peuvent être linéaires ou branchés. On préfère les hydrocarbures aliphatiques ou oléfiniques en Cl à C4, et notamment ceux en C2 ou C3. L'acétylène peut également convenir. Parmi les hydrocarbures aromatiques qui peuvent être utilisés figure le toluène qui, mélangé à du ferrocène, conduit, selon les constatations des présents inventeurs, à la formation de nanotubes en carbone alignés sur un substrat de SiC. Il est connu de l'article Evidence of Sequential Lift in Growth of Aligned Multiwalled Carbon Nanotube Multilayers par M. Pinault et al., Nano Letters Vol. 5 N 12, p. 2394-2398 (2005)) que la technique de CVD (Chemical Vapor Deposition) à partir d'aérosols contenant un mélange de benzène ou toluène et ferrocène conduit sur un substrat de silicium à la formation de nanotubes de carbone à parois multiples alignés. The hydrocarbon is an aliphatic, olefinic, acetylenic or aromatic C1 to C hydrocarbon. The aliphatic, olefinic or acetylenic hydrocarbons may be linear or branched. C 1 to C 4 aliphatic or olefinic hydrocarbons, especially those of C 2 or C 3, are preferred. Acetylene may also be suitable. Among the aromatic hydrocarbons that can be used is toluene which, mixed with ferrocene, leads, according to the findings of the present inventors, to the formation of carbon nanotubes aligned on an SiC substrate. It is known from the article Evidence of Sequential Lift in Growth of Aligned Multiwalled Carbon Nanotube Multilayers by M. Pinault et al., Nano Letters Vol. 5 N 12, p. 2394-2398 (2005)) that the CVD technique (Chemical Vapor Deposition) from aerosols containing a mixture of benzene or toluene and ferrocene leads on a silicon substrate to the formation of aligned multiwall carbon nanotubes.
Dans le cadre de la présente invention, un mélange gazeux comprenant au moins un hydrocarbure et l'hydrogène est utilisé. La température de la réaction doit être comprise entre 300 C et 1000 C, et se situe préférentiellement entre 600 C et 800 C. Ainsi on obtient des nanofibres ou nanotubes de carbone. Pour obtenir des nanofibres de SiC, une troisième étape est nécessaire : In the context of the present invention, a gaseous mixture comprising at least one hydrocarbon and hydrogen is used. The temperature of the reaction must be between 300 ° C. and 1000 ° C., and is preferably between 600 ° C. and 800 ° C. Thus, nanofibers or carbon nanotubes are obtained. To obtain SiC nanofibers, a third step is necessary:
(c) Transformation des nanotubes ou nanofibres en carbone en nanotubes et nanofibres de SiC. (c) Transformation of carbon nanotubes or nanofibers into nanotubes and nanofibres of SiC.
Dans cette étape optionnelle, on fait réagir les nanotubes ou nanofibres de carbone avec une vapeur de SiO. Pour obtenir du (3-SiC, la température de réaction se situe avantageusement entre 1000 C et 1500 C, préférentiellement entre 1050 C et 1400 C, et encore plus préférentiellement entre 1150 C et 1350 C. En fonction de la durée de la réaction, une conversion partielle ou complète des 15 nanotubes ou nanofibres de carbone en nanofibres de SiC, et notamment du 13-SiC, peut être obtenue. In this optional step, the carbon nanotubes or nanofibers are reacted with an SiO 2 vapor. To obtain (3-SiC, the reaction temperature is advantageously between 1000 ° C. and 1500 ° C., preferably between 1050 ° C. and 1400 ° C., and even more preferentially between 1150 ° C. and 1350 ° C. Depending on the duration of the reaction, a partial or complete conversion of the carbon nanotubes or nanofibers into SiC nanofibers, and in particular 13-SiC, can be obtained.
Ainsi, les étapes (a) et (b), optionnellement suivies d'une étape (c), conduisent à un nouveau produit composite comportant un substrat poreux de SiC avec des nanotubes 20 ou nanofibres de carbones, et / ou des nanofibres de SiC. Ces nanotubes ou nanofibres peuvent être alignés, en utilisant comme hydrocarbure à l'étape (b) un mélange formé d'un hydrocarbure aromatique, de préférence de toluène, et de ferrocène. Un produit particulièrement préféré est une mousse de 13-SiC avec une surface spécifique d'au moins 10 m2/g comportant des nanofibres ou nanotubes de carbone, ou 25 des nanofibres de SiC. Ce nouveau produit composite peut être utilisé comme catalyseur ou support de catalyseur. Thus, steps (a) and (b), optionally followed by a step (c), lead to a new composite product comprising a porous SiC substrate with carbon nanotubes or nanofibers, and / or SiC nanofibers. . These nanotubes or nanofibers may be aligned, using as hydrocarbon in step (b) a mixture of an aromatic hydrocarbon, preferably toluene, and ferrocene. A particularly preferred product is a 13-SiC foam with a surface area of at least 10 m 2 / g comprising carbon nanofibers or nanotubes, or SiC nanofibers. This new composite product can be used as catalyst or catalyst support.
Dans une variante du procédé selon l'invention, on dépose les nanotubes ou nanofibres 30 non pas sur un substrat poreux de SiC, mais sur un précurseur d'un tel substrat poreux de SiC. Dans cette variante, l'étape (a) comprend la préparation d'un précurseur d'un substrat poreux de SiC par infiltration d'une mousse de polymère carbonisable avec un mélange liquide comprenant une résine thermodurcissable et de la poudre de silicium, suivi du séchage de la mousse infiltrée, suivi de la polymérisation de la résine, et suivi de la carbonisation de la résine et de la mousse. La résine thermodurcissable peut être pure ou diluée dans un solvant approprié, tel que l'éthanol, l'acétone ou un autre solvant organique adéquat. Cela permet d'ajuster sa viscosité, ce qui favorise son mélange avec la poudre de silicium et son infiltration dans la mousse polymère. Comme résine thermodurcissable, on peut utiliser par exemple les résines phénoliques ou furfuryliques. Comme mousse de polymère, on utilise avantageusement une mousse alvéolaire de polyuréthane. Cette mousse peut par exemple présenter une structure macroscopique ouverte dont le diamètre moyen est sélectionné entre environ 600 m et 4500 m. Après infiltration, la mousse peut être mise à sécher à l'air ambiant. La température de polymérisation se situe typiquement entre 130 C et 200 C, et la température de carbonisation entre 500 C et 900 C. Une température d'environ 800 C est particulièrement avantageuse. On préfère effectuer ce traitement sous atmosphère d'argon. Ainsi, on obtient un squelette de carbone qui forme le précurseur de SiC. L'incorporation dans ce précurseur de SiC d'un catalyseur de croissance de nanotubes ou nanofibres peut se faire par imprégnation avec une solution aqueuse (possiblement mélangée avec un alcool, tel que l'éthanol) d'un sel de nickel, de fer, de cobalt, ou d'un mélange binaire ou ternaire de ces trois éléments ; ce sel est un précurseur de phase active. A titre d'exemple, on peut déposer un sel de nickel, typiquement du Ni(NO3)2. Une charge métallique comprise entre 0, 1% et 10%, et préférentiellement comprise entre 0,2% et 5% (pourcent massique) est avantageuse. On sèche, on calcine, et on transforme le précurseur de phase active en phase active, comme décrit ci-dessus. In a variant of the process according to the invention, the nanotubes or nanofibers 30 are deposited not on a porous SiC substrate, but on a precursor of such a porous SiC substrate. In this variant, step (a) comprises the preparation of a precursor of a porous SiC substrate by infiltration of a carbonizable polymer foam with a liquid mixture comprising a thermosetting resin and silicon powder, followed by drying the infiltrated foam, followed by the polymerization of the resin, and monitoring the carbonization of the resin and the foam. The thermosetting resin may be pure or diluted in a suitable solvent, such as ethanol, acetone or other suitable organic solvent. This allows to adjust its viscosity, which promotes its mixing with the silicon powder and its infiltration into the polymer foam. As the thermosetting resin, it is possible to use, for example, phenolic or furfuryl resins. As the polymer foam, a foam of polyurethane is advantageously used. This foam may for example have an open macroscopic structure whose average diameter is selected between about 600 m and 4500 m. After infiltration, the foam can be dried in ambient air. The polymerization temperature is typically between 130 ° C. and 200 ° C., and the carbonization temperature is between 500 ° C. and 900 ° C. A temperature of approximately 800 ° C. is particularly advantageous. It is preferred to carry out this treatment under an argon atmosphere. Thus, a carbon skeleton is obtained which forms the precursor of SiC. The incorporation into this precursor of SiC of a growth catalyst of nanotubes or nanofibers can be done by impregnation with an aqueous solution (possibly mixed with an alcohol, such as ethanol) of a salt of nickel, iron, cobalt, or a binary or ternary mixture of these three elements; this salt is an active phase precursor. By way of example, a nickel salt, typically Ni (NO 3) 2, can be deposited. A metal charge of between 0.1% and 10%, and preferably between 0.2% and 5% (mass percent) is advantageous. The active phase precursor is dried, calcined and converted to the active phase as described above.
Sur ce matériau, on fait croître dans l'étape (b), comme décrit ci-dessus, des nanotubes ou nanofibres de carbone. Pour obtenir un matériau composite comportant des nanotubes ou nanofibres de SiC sur un substrat de (3-SiC, on transforme dans l'étape (c) à la fois les nanotubes ou nanofibres de carbone et le précurseur de SiC en 13-SiC, par un traitement thermique à une température comprise entre 1200 C et 1500 C, et préférentiellement entre 1300 C et 1400 C. Une température d'environ 1350 C pendant une durée comprise entre 0,5 et 5 heures, et typiquement d'une heure, convient. On préfère travailler sous argon. Dans ces conditions de procédé, la poudre de silicium réagit avec le carbone du squelette de carbone ; cette réaction implique probablement des vapeurs de SiO générées in situ, qui diffusent du coeur de la mousse de carbone vers l'extérieur. Cette variante du procédé présente l'avantage de désactiver les particules de nickel ayant servi comme catalyseur de croissance des nanofibres ou nanotubes de carbone, car lesdites particules sont carburées ou siliciurées dans les conditions de l'étape (c). Ces particules désactivées n'interféreront pas avec l'utilisation ultérieure du composite en tant que catalyseur ou support de catalyseur. On this material, carbon nanotubes or nanofibers are grown in step (b) as described above. In order to obtain a composite material comprising SiC nanotubes or nanofibers on a (3-SiC) substrate, carbon nanotubes or nanofibers and the SiC precursor in 13-SiC are converted in step (c) by a heat treatment at a temperature of between 1200 ° C. and 1500 ° C., and preferably between 1300 ° C. and 1400 ° C. A temperature of approximately 1350 ° C. for a period of between 0.5 and 5 hours, and typically of one hour, is appropriate It is preferred to work under argon under these process conditions, the silicon powder reacts with the carbon of the carbon skeleton, this reaction probably involves in situ generated SiO vapors which diffuse from the core of the carbon foam to the carbon skeleton. This variant of the process has the advantage of deactivating the nickel particles having served as a growth catalyst for nanofibers or carbon nanotubes, since said particles are carburized or silicided in the process. s conditions of step (c). These deactivated particles will not interfere with the subsequent use of the composite as a catalyst or catalyst support.
Avantages et utilisation de l'invention L'invention présente de nombreux avantages. La croissance des nanotubes ou nanofibres peut remplir largement les pores, et notamment les macropores, du support, et notamment dans le cas des mousses de e-SiC. On constate que la perte de charge d'un flux gazeux ou liquide occasionné par la présence des nanotubes ou nanofibres est très faible. Par ailleurs, les nanotubes ou nanofibres ne se détachent pas facilement de leur support, comme on le constate par exemple lors d'un essai de sonication. Advantages and Use of the Invention The invention has many advantages. The growth of nanotubes or nanofibers can largely fill the pores, and in particular the macropores, of the support, and in particular in the case of e-SiC foams. It is noted that the pressure drop of a gaseous or liquid flow caused by the presence of nanotubes or nanofibers is very low. In addition, the nanotubes or nanofibers are not easily detached from their support, as can be seen for example during a sonication test.
Le produit composite selon l'invention peut être utilisé comme support de catalyseur, après le dépôt d'une phase active appropriée. A titre d'exemple, on peut déposer, par des méthodes connues, des particules de palladium sur le support. On peut catalyser des réactions chimiques en phase gazeuse ou en phase liquide, telles que des réactions d'hydrogénation d'aldéhydes. L'hydrogénation du cinnamaldéhyde en phase liquide est un exemple d'une réaction qui peut être catalysée par le produit composite selon l'invention, après dépôt d'une phase active appropriée. Le catalyseur est très stable. The composite product according to the invention can be used as a catalyst support after the deposition of a suitable active phase. By way of example, palladium particles can be deposited by known methods on the support. Chemical reactions in the gas phase or in the liquid phase can be catalyzed, such as hydrogenation reactions of aldehydes. The hydrogenation of cinnamaldehyde in the liquid phase is an example of a reaction that can be catalyzed by the composite product according to the invention, after deposition of a suitable active phase. The catalyst is very stable.
Le produit composite selon l'invention peut aussi être utilisé directement comme catalyseur. S'agissant d'une pièce monolithique de mousse de SiC, la séparation du catalyseur et des produits de réaction ne pose aucun problème. The composite product according to the invention can also be used directly as a catalyst. Being a monolithic piece of SiC foam, the separation of the catalyst and the reaction products is not a problem.
Les exemples qui suivent illustrent des modes de réalisation de l'invention, mais ne limitent pas sa portée. The following examples illustrate embodiments of the invention, but do not limit its scope.
Exemples•Examples •
Exemple 1 : Préparation d'un produit Nanofibres de carbone sur mousse de (3-SiC selon l'invention EXAMPLE 1 Preparation of a Carbon Nanofiber Product on (3-SiC) Foam According to the Invention
Une mousse de 13-SiC avec une taille moyenne de macropores d'environ 1700 m et une surface spécifique de 10 m2/g, préparée selon les techniques connues, a été imprégnée avec une solution aqueuse de Ni(NO3)2 de manière à obtenir une charge de nickel de 1% massique dans la mousse de 5-SiC. La mousse imprégnée a été séchée pendant 2 heures à 100 C dans un four, et ensuite calcinée à l'air à 400 C. Une réduction par l'hydrogène à été effectuée à cette température in situ. Ensuite, on a remplacé l'hydrogène par un mélange de C2H6 / H2 (débit : 60 ml min-1 / 40 ml min-1) et on a augmenté la température de réaction de 400 C à 750 C avec une vitesse de chauffage de 20 C min-1. On a effectué la synthèse de nanofibres de carbone pendant 2 heures dans ces conditions, et ensuite on a laissé refroidir le réacteur à la température ambiante, tout en maintenant le flux de gaz C2H6 / H2. Le produit composite Nanofibre de carbone sur mousse de (3-SiC ainsi obtenu contenait 28% massique de nanofibres de carbone, et avait la même apparence et morphologie et le même comportement mécanique que la mousse de départ, sauf que la couleur grise-verte du (3-SiC initial s'était transformée en noir. L'observation microscopique de la morphologie par microscopie électronique à balayage (SEM, à l'aide d'un microscope Jeol TMde type JSM-6700F équipé d'une caméra CCD, avec une tension d'accélération de 3 kV sur des surfaces revêtues d'un film d'or) montre que toutes les cavités de la mousse de 13-SiC initiale étaient remplies par un réseau dense et enchevêtré de nanofibres de carbone. La surface spécifique de ce produit composite était de 52 m2/g, alors que la mousse de (3-SiC de départ n'avait qu'une surface spécifique d'environ 10 m2/g. On estime la surface spécifique des nanofibres de carbone de l'ordre de 140 m2/g. L'analyse par microscopie électronique par transmission (TEM, à l'aide d'un microscope Topcon TM de type 002B avec une tension d'accélération de 200 kV et une résolution de point à point de 0,17 nm, sur des échantillons dispersés dans de l'éthanol sous agitation ultrasonique, dont une goutte a ensuite été déposée sur une grille de cuivre revêtue de 8 carbone) montre la quasi-absence de nanoparticules de carbone : on ne voit que des nanofibres de carbone qui forment une couche homogène et représentent un réseau enchevêtré de fibres de diamètre sensiblement constant de l'ordre de 40 nm et d'une longueur pouvant atteindre quelques douzaines de micromètres, qui sont reliées entre elles par des ponts. Ces ponts sont probablement la cause de la grande résistance mécanique de cet enchevêtrement de nanofibres, qui est une propriété propice pour leur utilisation en catalyse, où l'on souhaite disposer d'un catalyseur présentant une bonne stabilité mécanique sous un flux gazeux ou liquide. On note par ailleurs l'absence de pores dans les nanofibres ; cela les rend intéressants comme catalyseur de support de catalyseur, surtout en milieu liquide où les phénomènes de diffusion deviennent prédominants. On a mesuré la perte de charge dans le composite selon l'invention. Les résultats sont indiqués sur la figure 1. Cette perte de charge est très faible, alors que l'on pourrait s'attendre à une perte de charge importante lorsque l'on remplit les macropores du substrat (mousse de a-SiC) avec un matériau nanoscopique. On constate également que la macroporosité de la mousse de (3-SiC initiale ne diminue que très peu lors de la croissance des nanofibres de carbone : de 0,9 (i.e. 90% du volume apparent vide) à 0,85 pour un taux de nanofibres de carbone de 20% massique. On a déterminé l'ancrage des nanofibres sur leur support de mousse de (3-SiC par un essai de sonication pendant 30 minutes. On n'a pas observé de perte de nanofibres lors de cet essai. A 13-SiC foam with an average macropore size of about 1700 m and a surface area of 10 m 2 / g, prepared according to known techniques, was impregnated with an aqueous solution of Ni (NO 3) 2 in order to obtain a nickel load of 1% by weight in the 5-SiC foam. The impregnated foam was dried for 2 hours at 100 ° C. in an oven and then calcined in air at 400 ° C. A reduction with hydrogen was carried out at this temperature in situ. Then, the hydrogen was replaced by a mixture of C2H6 / H2 (flow rate: 60 ml min-1/40 ml min-1) and the reaction temperature was increased from 400 C to 750 C with a heating rate of 20 C min-1. The carbon nanofibers were synthesized for 2 hours under these conditions, and then the reactor was allowed to cool to room temperature while maintaining the C2H6 / H2 gas flow. The (3-SiC) carbon nanofiber composite product thus obtained contained 28% by mass of carbon nanofibers, and had the same appearance and morphology and mechanical behavior as the starting foam, except that the gray-green color of the (3-SiC initial was transformed into black.) The microscopic observation of the morphology by scanning electron microscopy (SEM, using a JSM-6700F type Jeol TM microscope equipped with a CCD camera, with a 3 kV acceleration voltage on gold film coated surfaces) shows that all the cavities of the initial 13-SiC foam were filled by a dense and intertwined network of carbon nanofibers. composite product was 52 m2 / g, whereas the starting (3-SiC) foam had a specific surface area of only about 10 m2 / g.The specific surface area of the carbon nanofibers of the order of 140 m2 / g The analysis by electron microscopy by transmission using a Topcon TM 002B microscope with a 200 kV acceleration voltage and a point-to-point resolution of 0.17 nm, on ethanol dispersed samples. ultrasonic stirring, of which one drop was then deposited on a carbon-coated copper grid) shows the virtual absence of carbon nanoparticles: we only see carbon nanofibers which form a homogeneous layer and represent a tangled network of fibers. of substantially constant diameter of the order of 40 nm and a length of up to a few dozen micrometers, which are interconnected by bridges. These bridges are probably the cause of the high mechanical strength of this entanglement of nanofibers, which is a propitious property for their use in catalysis, where it is desired to have a catalyst having good mechanical stability under a gaseous or liquid flow. There is also the absence of pores in nanofibers; this makes them attractive as a catalyst support catalyst, especially in a liquid medium where diffusion phenomena become predominant. The pressure drop in the composite according to the invention was measured. The results are shown in FIG. 1. This pressure drop is very low, whereas one would expect a significant pressure drop when filling the macropores of the substrate (α-SiC foam) with a nanoscopic material. It is also noted that the macroporosity of the initial (3-SiC) foam only decreases very little during the growth of the carbon nanofibers: from 0.9 (ie 90% of the apparent empty volume) to 0.85 for a rate of 20% carbon nanofibers The nanofibers were anchored to their (3-SiC) foam support by a sonication test for 30 minutes, and no loss of nanofibers was observed during this test.
Exemple 2 : Préparation d'un produit Nanofibres de SiC sur mousse de 13-SiC selon l'invention 25 Dans une variante du procédé décrit à l'exemple 1, on a, au lieu de laisser refroidir le réacteur à la température ambiante, augmenté la température à 1200 C. A cette température, la génération in situ de vapeur de SiO permet de transformer les nanofibres de carbone en nanofibres de SiC. La température de 1200 C a été pendant 4 30 heures à 1200 C. Cette réaction étant accompagnée de la formation de CO et CO2, on a enlevé ces gaz constamment par pompage. La température de réaction de 1200 C n'est pas suffisante pour provoquer la transformation de la mousse de (3-SiC en a-SiC, une transformation qui engendrerait io une perte très significative de surface spécifique. On a trouvé effectivement que la surface spécifique d'une a-SiC formée à une température appropriée, plus élevée, est de l'ordre de 0,1 m2/g à 1 m2/g. L'observation microscopique de ce composite a été effectué dans des conditions similaires à celles décrites dans l'exemple 1. On a constaté que les nanofibres de SiC étaient formées d'un empilement de nanoparticules de SiC le long de l'axe de la nanofibre, ces nanoparticules ayant une taille de l'ordre de 30 nm à 60 nm, et le diamètre des nanofibres de SiC étant un peut plus élevée que celle des nanofibres de carbone dont elles sont issues. EXAMPLE 2 Preparation of a SiC Nanofiber Product on a 13-SiC Foam According to the Invention In a variant of the process described in Example 1, instead of allowing the reactor to cool to room temperature, it was increased the temperature at 1200 C. At this temperature, the in situ generation of SiO vapor makes it possible to transform the carbon nanofibers into SiC nanofibers. The temperature of 1200 C was for 4 hours at 1200 C. This reaction being accompanied by the formation of CO and CO2, these gases were constantly removed by pumping. The reaction temperature of 1200 ° C. is not sufficient to cause the transformation of the (3-SiC) foam into α-SiC, a transformation which would give rise to a very significant loss of specific surface area. an α-SiC formed at a suitable, higher temperature is in the range of 0.1 m 2 / g to 1 m 2 / g microscopic observation of this composite was carried out under conditions similar to those described. in Example 1. It was found that the SiC nanofibers were formed of a stack of SiC nanoparticles along the nanofiber axis, these nanoparticles having a size of the order of 30 nm to 60 nm, and the diameter of the SiC nanofibers being a little higher than that of the carbon nanofibers from which they are derived.
Exemple 3 : Utilisation d'un produit selon l'invention pour catalyser une réaction chimique en phase liquide Example 3 Use of a Product According to the Invention to Catalyze a Chemical Reaction in the Liquid Phase
On a effectué une hydrogénation du cinnamaldéhyde en phase liquide dans un réacteur autoclave en verre d'un volume effectif de 1000 ml équipé d'un agitateur mécanique. La solution de réaction contenait 500 ml de dioxane et 10 ml de cinnamaldéhyde. On a utilisé le dioxane plutôt qu'un alcool pour éviter une réaction homogène susceptible de conduire à des produits secondaires lourds et indésirables. Le catalyseur mousse (diamètre 30 mm, épaisseur 15 mm) a été fixé sur une tige en verre et a été utilisé comme agitateur. Afin d'éliminer toute trace d'oxygène dans la solution, on a fait buller de l'argon (débit 50 ml min-1) à la température ambiante à travers cette phase liquide, tout en agitant vigoureusement (environ 500 tours mir 1). Ensuite on a augmenté la température jusqu'à 80 C avec une vitesse de chauffage d'environ 10 C mir-s, et on a remplacé le flux d'argon par un flux d'hydrogène de même débit. On a suivi tout au long de la réaction la concentration en cinnamaldéhyde et la distribution des différents produits en fonction du temps par chromatographie en phase gazeuse à l'aide d'un chromatographe de type VarianTM 3800 équipé d'une colonne capillaire Pona revêtue de méthyl siloxane et d'un détecteur à ionisation par flamme (en anglais Flame lonization Detector , FID), qui a analysé des microéchantillons prélevées périodiquement et diluées dans du dioxane. On a calibré les chromatogrammes à l'aide de concentrations connues de substances pures de cinnamaldéhyde, alccol cinnamique, 3phényl propanol et 3-phénylpropénal. Hydrogenation of the cinnamaldehyde in the liquid phase was carried out in a glass autoclave reactor of an effective volume of 1000 ml equipped with a mechanical stirrer. The reaction solution contained 500 ml of dioxane and 10 ml of cinnamaldehyde. Dioxane was used rather than an alcohol to avoid a homogeneous reaction that could lead to unwanted and heavy secondary products. The foam catalyst (diameter 30 mm, thickness 15 mm) was fixed on a glass rod and was used as an agitator. In order to eliminate all traces of oxygen in the solution, argon (flow rate 50 ml min-1) was bubbled at room temperature through this liquid phase, while stirring vigorously (approximately 500 turns mir 1). . Then the temperature was increased to 80 C with a heating rate of about 10 C mir-s, and the argon stream was replaced by a flow of hydrogen of the same rate. The cinnamaldehyde concentration and the distribution of the various products as a function of time were monitored throughout the reaction by gas chromatography using a VarianTM 3800 chromatograph fitted with a methyl-coated Pona capillary column. siloxane and a flame ionization detector (Flame lonization Detector, FID), which analyzed microsamples taken periodically and diluted in dioxane. The chromatograms were calibrated using known concentrations of pure substances of cinnamaldehyde, cinnamic alcohol, 3-phenylpropanol and 3-phenylpropenal.
H2 Ph ' O > PhOH H2 H2 PhO > PhOH H2 Ph 'O> PhOH H2 H2 PhO> PhOH
Cette réaction complexe implique une hydrogénation de liaisons C=C et C=0 et passe par plusieurs produits intermédiaires, notamment l'alcool cinnamique (en haut à droite du schéma réactionnel) et l'hydrocinnalaldéhyde (en bas à gauche du schéma réactionnel), qui peuvent ensuite être convertis en 3-phényl-1-propanol (en bas à droite du schéma réactionnel). This complex reaction involves a hydrogenation of C = C and C = O bonds and passes through several intermediate products, in particular cinnamic alcohol (top right of the reaction scheme) and hydrocinnalaldehyde (bottom left of the reaction scheme), which can then be converted to 3-phenyl-1-propanol (bottom right of the reaction scheme).
Exemple 4 : Préparation d'un produit composte nanofibres de SiC sur mousse de 13- SiC selon l'invention EXAMPLE 4 Preparation of a SiC Nanofiber Compound Product on a 13-SiC Foam According to the Invention
On a infiltré une mousse alvéolaire de polyuréthane avec un mélange liquide comprénant une résine furfurylique (diluée dans de l'éthanol pour ajuster sa viscosité) et de la poudre de silicium. Après séchage, on a procédé a une polymérisation à environ 160 C et à une carbonisation à une température d'environ 800 C sous argon. On a ainsi obtenu un squelette carboné. Celui-ci est imprégné avec une solution aqueuse de Ni(NO3)2 de manière à obtenir une charge de nickel de 1% (pourcent massique). Ce matériau a ensuite été traité comme à l'exemple 1 afin d'obtenir des nanofibres de carbone sur le précurseur carboné. Le matériau composite ainsi obtenu a été placé à 1360 C sous 1 bar d'argon pendant 1 h afin de transformer le squelette carboné en 13-SiC. A polyurethane foam was infiltrated with a liquid mixture comprising a furfuryl resin (diluted in ethanol to adjust its viscosity) and silicon powder. After drying, polymerization was carried out at about 160 ° C. and carbonization at a temperature of about 800 ° C. under argon. There was thus obtained a carbon skeleton. This is impregnated with an aqueous solution of Ni (NO3) 2 so as to obtain a nickel load of 1% (mass percent). This material was then treated as in Example 1 in order to obtain carbon nanofibers on the carbon precursor. The composite material thus obtained was placed at 1360 ° C. under 1 bar of argon for 1 hour in order to transform the carbon skeleton into 13-SiC.
Claims (11)
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JP2010504792A JP2010526009A (en) | 2007-05-02 | 2008-04-30 | Nanotube or nanofiber composite on β-SiC foam |
PCT/FR2008/000617 WO2008152221A2 (en) | 2007-05-02 | 2008-04-30 | Composite consisting of nanotubes or nanofibres on a β-sic film |
EP08805530A EP2144698A2 (en) | 2007-05-02 | 2008-04-30 | Composite consisting of nanotubes or nanofibres on a b-sic film |
US12/598,528 US20100297428A1 (en) | 2007-05-02 | 2008-04-30 | Composit consisting of nanotubes or nanofibres on a b-sic film |
KR1020097025124A KR20100056998A (en) | 2007-05-02 | 2008-04-30 | COMPOSITE CONSISTING OF NANOTUBES OR NANOFIBRES ON A β-SIC FILM |
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US20100252450A1 (en) * | 2008-04-09 | 2010-10-07 | Riehl Bill L | Electrode and sensor having carbon nanostructures |
TWI499553B (en) * | 2009-09-14 | 2015-09-11 | Univ Nat Cheng Kung | Carbon nanotube and method for producing the same |
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JP3183845B2 (en) * | 1997-03-21 | 2001-07-09 | 財団法人ファインセラミックスセンター | Method for producing carbon nanotube and carbon nanotube film |
JP2000281324A (en) * | 1999-03-31 | 2000-10-10 | Toshiba Corp | Hydrogen occlusion body |
JP3912583B2 (en) * | 2001-03-14 | 2007-05-09 | 三菱瓦斯化学株式会社 | Method for producing oriented carbon nanotube film |
FR2832649B1 (en) * | 2001-11-23 | 2004-07-09 | Sicat | COMPOSITES BASED ON CARBON NANOTUBES OR NANOFIBERS DEPOSITED ON AN ACTIVE SUPPORT FOR CATALYSIS APPLICATION |
JP3848584B2 (en) * | 2002-02-22 | 2006-11-22 | 財団法人ファインセラミックスセンター | Method for producing carbon nanotube |
JP3781732B2 (en) * | 2003-03-20 | 2006-05-31 | 株式会社東芝 | Carbon nanotube manufacturing method, semiconductor device manufacturing method using carbon nanotube, and carbon nanotube manufacturing apparatus |
FR2858980B1 (en) * | 2003-08-19 | 2006-02-17 | Inst Francais Du Petrole | USE OF A CATALYST COMPRISING A SILICON B FUEL SUPPORT IN A SELECTIVE HYDRODESULFURATION PROCESS |
US20050112048A1 (en) * | 2003-11-25 | 2005-05-26 | Loucas Tsakalakos | Elongated nano-structures and related devices |
JP2005255439A (en) * | 2004-03-10 | 2005-09-22 | Japan Fine Ceramics Center | Nano, micro and macro multiplex structured porous body and method of manufacturing the same |
JP2005263564A (en) * | 2004-03-19 | 2005-09-29 | Toyota Central Res & Dev Lab Inc | Method for manufacturing carbon nanotube |
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2007
- 2007-05-02 FR FR0703155A patent/FR2915743A1/en not_active Withdrawn
- 2007-07-03 FR FR0704805A patent/FR2915745B1/en not_active Expired - Fee Related
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- 2008-04-30 JP JP2010504792A patent/JP2010526009A/en active Pending
- 2008-04-30 EP EP08805530A patent/EP2144698A2/en not_active Withdrawn
- 2008-04-30 KR KR1020097025124A patent/KR20100056998A/en not_active Application Discontinuation
- 2008-04-30 WO PCT/FR2008/000617 patent/WO2008152221A2/en active Application Filing
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WO2009098393A3 (en) * | 2007-11-30 | 2009-11-05 | Centre National De La Recherche Scientifique | Chemical reactor with nanometric superstructure |
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FR2915745B1 (en) | 2009-08-21 |
US20100297428A1 (en) | 2010-11-25 |
WO2008152221A3 (en) | 2009-02-19 |
WO2008152221A8 (en) | 2010-03-04 |
FR2915745A1 (en) | 2008-11-07 |
JP2010526009A (en) | 2010-07-29 |
EP2144698A2 (en) | 2010-01-20 |
WO2008152221A2 (en) | 2008-12-18 |
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